Dihalo-alkenyl alkenoates



Patented Apr. 22, 1952 2,594,184

UNITED STATES PATENT OFFICE DIHALO-ALKENYL ALKENOATES Elbert C. Ladd,Passaic, N. J assignor to United StatesRubber Company, New York, N. Y.,a corporation of New Jersey No Drawing. Application December 30, 1948,Serial No. 68,393

- 3 Claims. (01. 260-486) The invention relates to a new class of estersmmmdicals consisting of the esters of ethylenically unsatu- (1- OctCm=crn Ci3C-CHi' H2- -1 rated monoand poly-carboxylic acids with 3,3- ,ggggg dihalogeno-Z-propen-1-ols of the formula X2C=CHCHR--OH wherein eachX is fluorine, chlorine, or bromine, and R is selected from the class ofhydrogen and hydrocarbon. t 1

My new polyolefinic esters can be readily pre (H) 30*CHPCH7MM pared bythe reaction of a 3,3-dihalogeno-2- CIFOTCHPOHTCI proper y] halideX2C=CH CHR Y h i (2b) GlFzCCII1--CH -Ol alcoholic KOH I each X and Yisone of the halogens fluorine, 2 IL chlorine, and bromine, with anolefinic monoor e polycarboxylic acid or the alkali metal salt (H)cmoqmzcm +361; F'ZC2CHHCHWC1 thereof. Indeed in this reaction I havefound o=cH-cnc1 N -oco or that the 3,3-dihalogeno-2-propenyl halidesdis- (0 d) h 2 i play an unexpectedly high degree of reactivity in 2 2 Icomparison with the next higher homologs, i. e., (H) UWMOHWCHQAH SbFaChthe 4,4-dichloro-3-butenyl halides. F3C"'CH2 CH?01 The3,3-dihalogeno-2-propenyl halide starting (34) F3C"CH1"CH@"G1 9 KOHmaterials employed in my invention are in the FJCCH=CHI main readilyobtainable through the selective FGCI'K and partial dehydrohalogenationof compounds (3'6) F30CH=C'H MCSCEFCHFF of the formula X3CCI-I z-CHRY,which are co ric= m I r1= the 1:1 adducts resulting from thefree-radical- 2 =CH-CHz-0C ocrn-h catalyzed (e. g., peroxide-catalyzed)reactions of tree olefinic compounds CH2=CHR with tetrahalo- 4- 0011; on=CH B1-ClC-C-H on B:' genomethanes where each X and Y is 2 2 1 2 2chlorine or bromine, provided that Y is chlorine BrCl2C CH2*GH2 Br swamA only when every X is chlorine, that is, when the (IMG CHPCHTBtetrahalogenomethane CX'aY contains at least C1 C1FC=CH CH one bromineatom, it is invariably a bromine atom c) 2 A 2 2 which splits ofi andadds as a separate unit to the (M) (FC=CH CH Br olefinic compound. The1:1 adducts are best made by reacting one molar proportion of the r golefinic compound CH2=CHR with a consider- (5.) m 011 011, 1BrzClCCHq-CHz-Bi' able excess, preferably at least three molar pro-FeCl;

portions, of the tetrahalogenomethane at 20-200 (H) BnOlC-CfirCm-Br C.in the presence of a peroxidic compound, e. g., (5-u) Bro1o=oH-orn1ar N-OOOCH: benzoyl peroxide, present in an amount on the BrCIC=CHCHIOCOCHIorder of from 1 to 5% by weight of the amount Alternatively the 3 3diha10geno 2 pr()peny1 of olefinic compound. The selective, partialdehalides can be hydrolyzed t th corresponding hydrohalogenation of the1:1 adducts may be 45 3 3 diha10gen() 2-propen-1-()1s which can then becarried out by the process disclosed in the app reacted. with theolefinic acid or derivatives hycation of Ladd et al., Serial No. 24,446,filed April drglyzable thereto, alkyl esters Such as t 1943- Thefiorresponding -c p u ds methyl ester, to form the new esters, thus:

(i. e., where X and/or Y is fluorine) are best prealkali pared bytreating such adducts with a fluorinat- (6a) C12C=CHCHzCl 11,0 c1,c--cH- oH,-oH ing agent, e. g., SbFsClz, as disclosed in my ap- CHFCEPOOOHplication, Serial No. 54,203, filed October 12, 1948, OIZC=CH GHR O COCH=CHI now abandoned. The preparation of these start- (H) 012 C: CH? o HCHFC (CHaHJ CH ing materials and their use in my invention can beillustrated as follows: (CH)CH The new esters may also be made by esterinterchange, thus:

l-nonene and 3-chloro-1,1-difluoro-3-phenyl-1- propene.

Of the olefinic acid reactants employed in my invention the Z-alkenoicand the Z-aIkene-polyoic acids are preferred, including themcnocarboxylic acids such as acrylic, methacrylic, ethacrylic,chloroacrylic, trichloracrylic, crotonic, cinnamic and tiglic acids, andthe polycarboxylic acids such as maleic, chloromaleic, fumaric,itaconic, mesaconic, citraccnic, aconitic, 3,4-dichlorodihydromuconic,carbic, and 3,4,5,6-tetrachloro 3,6 endo(dichloromethylene)tetrahydrophthalic acids. As indicated above, these acids may beemployed in the form of their salts, preferably the alkali metal salts;e. sodium acrylate, potassium crotonate, and sodium maleate.

Illustrative of the new esters of my invention are3,3-dichloro-2-propenyl acrylate, bis (3,3- dichloro-Z-propenyl)maleate, bis(3,3-dichloro- Z-propenyl) fumarate, 3,3'lifluoro-2-propeny1acrylate, 3,3-dichloro-2-propenyl methacrylate, 3,3-difluoro-2-propenylchloroacrylate, and 3,3- dichloro-2-propenyl crotonate.

These new compounds are particularly useful in the preparation ofaddition-type polymers and copolymers, but they also find use in thepreparation and/or synthesis of pharmaceuticals, plasticizers andlubricating oil additives.

In the preparation of my new compounds, sub- 4 stantially equivalentquantities of the 1,3,S-trihalogeno-2-propenyl compound and the olefinicacid or its alkali metal salt are heated together at temperatures in therange of 25 C. to 130 C. or higher, but preferably at from C. to 100 C.until esterification has taken place, which may require from2 to 24hours. Diluents, e. g., alcohols, such as ethanol or butanol, may beemployed to homogenize the reaction mixture if necessary. The productscan be isolated by preferential extraction, and/or by fractionaldistillation, the latter process being preferably conducted in thepresence of a polymerization inhibitor, e. g.,, p-tert.-butylcatechol;

The following example discloses my invention in more detail. All partsare by weight.

Example A solution of 72.69 parts of 3,3-dichloro-2 propenyl chloride(i. 1,1,3-trichloropropene) and 50.0 parts of sodium acrylate in about240 parts .of aqueous ethanol is refluxed with stirring for 12 hours.The reaction mixture is then diluted with two volumes of water and theresulting non-aqueous layer is separated, dried, and fractionallydistilled to yield 13.4 parts of the new compound,3,3-dichlero-2-propenyl acrylate, B. 37-44 C./2 mm.; 11 1.4842; percentchlorine, 39.17 (theory, 41.11). This compound polymerizesspontaneously, albeit "slowly, at room temperature.

Having thus described my invention, what 1 claim and desire to protectby Letters Patent is:

l. A 3,3-dihalcgen0-2-propenyl ester of a 2 alkenoic acid.

2. A 3,3-dichloro-2-propenyl alkenoic acid.

3. 3,3-dichloro-2-propenyl acrylate.

ester of a 2- ELBERT C. LADD.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,296,823 Pollack Sept. 22, 19422,388,440 'Rehberg Nov. 5, 1945

1. A 3,3-DIHALOGENO-2-PROPENYL ESTER OF A 2ALKENOIC ACID.